Surface Science 62 (1977) 267-276

North-Holland Pubhshlng Company

S U R F A C E F R E E E N E R G I E S O F S O L I D METALS" E S T I M A T I O N FROM
LIQUID SURFACE TENSION MEASUREMENTS
W R TYSON
Ferrous Metals Section, Phystcal Metallurgy Research Laboratories, Canada Centre for Minerals
and Energy Technology, Department of Energy, Mines and Resources, Ottawa, Canada
and
W.A. M I L L E R
Department of Metallurgy and Matertals Sctence, Unwerslty of Toronto, Toronto, Canada
Recewed 25 May 1976, manuscript received m final form 24 September 1976

An equation is derived on semi-theoretical grounds which expresses the sohd-vapour surlace free energy as a function of the hquld surface tension and the sohd-hquld lnterfaclal free
energy A means of calculating rehable values for the sohd-hqmd energy ts presented, which
then allows an accurate estimate of sohd surface energy at the meltmg temperature, Tin, to be
made for the large number of elements for which dependable hqmd surface tension data exist
A method of esttmatmg surface entropy IS presented, and has been used to calculate the energies typical of "average ", high-index surfaces at temperatures ranging from 0 K to T m It is felt
that thls paper describes the most accurate method presently available for the calculation of
the surface energy of sohds In the absence of direct experimental measurement

1. Introduction
The surface energy o f solids IS an i m p o r t a n t physical p a r a m e t e r m controlling a
w~de range o f p h e n o m e n a , such as the stress for brittle fracture, the rate o f sIntering, and the g r o w t h rate during particle coarsening. F o r tlus reason, there have b e e n
m a n y attempts, both experimental and theoretical, to derive values o f the surface
free energy, summaries have been given recently by Blakely [1], LInford [2], and
Mykura [3] The available e x p e r i m e n t a l t e c h n i q u e s are difficult and usually Inaccurate, w i t h results from different workers o f t e n being In very p o o r agreement [4].
Theoretical m e t h o d s are strnflarly c o m p l i c a t e d , although there IS some h o p e that
recent advances wall produce reliable calculations b o t h for simple metals [5] and
for transition metals [6].
The e x p e r i m e n t a l d e t e r m i n a t i o n o f absolute values o f surface energy for any
t y p e o f interface is b o t h difficult and subject to n u m e r o u s errors, the most severe
267

268

W R Tyson, W A Mdler / Surface free energtes of sohd metals

of which IS usually lowering of the true lnterfaclal energy by surface-active contarmnants. These may be Introduced either as dissolved Impurity from within the
material or as an adsorbing species from the surrounding gaseous atmosphere
Nevertheless, surface free energy (surface tension) can be measured much more
accurately for hqutds than for solids (although not necessarily more easily), and
comprehensive tabulations of hquld-vapour surface tension 7LV are available for a
large number of elements [7]. It is the purpose of this paper to describe briefly how
the liquid surface tension data may be used to derive reliable estimates of "average"
sohd-vapour surface energies 7sv, the basis of the method will be analyzed In
greater detail elsewhere [8]

2. Estimation of 7SV/TLV at the melting point, Tm

Three mterfaclal free energies are revolved m solld-hquld-vapour equlhbrium
7sv, 3'LV, and the solld-lNuld lnterfaclal free energy 7SL In this section, we
attempt to deduce the relationships between these quantities m single component
systems
We may write one condition lmme&ately which follows from the well-known
observation that metals cannot normally be superheated above T m This Implies the
absence of a nucleation barrier for surface melting, hence
")'SV ~ "~LV + ')'SL

(1)

Note that any type of high energy defect in the sohd such as dislocations, grain
boundanes, surface steps, etc., may be able to nucleate melting without an energy
barrier In the present analysis however, we assume that a local region of a perfectly
flat, Infinite surface may also nucleate melting with no superheating, so that eq. (I)
may be applied.
At temperatures close to Tin, it would be expected that the sohd surface has a
structure which IS atomically rough If this roughening IS achieved without destroying the crystallographic nature of the surface, then the surface can be considered to
be "crystalline" If the roughening and atomic rearrangement is more severe, then
the state of the surface may be more akin to a liquid, and a surface "melting"
transition may occur below Tm The nature of the process which actually occur,
will be determined by the magnitudes of the various free energy changes.
Suppose that the surface were to remain crystalline up to T m Then crystallographic roughening would occur, with an associated surface free energy"yR. Suppose,
on the other hand, that surface melting were to occur at temperatures below Tm to
a depth sufficient for the surface layer to be considered as a bulk liquid with independent sohd-hquld and hquld-vapour Interfaces The surface free energy of such
a solid would be
7M =TLv +TsL +(GL

Gs) t ,

W R Tyson, W A Mdler / Surface free energies ofsohd metals

269

where GL, G S are the free energies per umt volume of the hqmd and sohd, respectively, and t is the depth of the lnterfaclal hqmd layer. At temperatures below Tm,
the last term increases the free energy and in order to minimize its magnitude t will
clearly be small, of the order of at most a few monolayer thicknesses. Hence, the
last term tends to zero at Tm, as (G L - Gs) tends to zero
Unfortunately, there are no expenmental data with which to estabhsh rehably
the structure of solid surfaces at temperatures close to T m. It is known from LEED
studies that metal surfaces are crystallme at temperatures well below Tm, but it Is
not known whether the surface melts before T m is reached. The state of the
surface, and hence 7sv, will be determined by the relative magnitudes of ?'R and
7M. As shown above, the surface energy of a solid covered by a thin molten layer
is "i'M = ")'SL + ")'LVat Tm, and so surface melting should take place at temperatures
equal to and slightly less than Tm unless 7R ~<7LV + 7SL- However, Eq. (1)
requires that the surface energy be equal to or greater than 7SL + 7LV- Therefore,
we conclude that at Tin,
7SV = ')'SL + "YLV ,

(2)

and the surface consists of either a thin hquld-llke layer or a crystallographically

roughened layer of the same energy.
The above analysis did not consider the posslbthty of an anisotroplc 3'sv at
Tm. Neither the crystaUographlc roughening nor the surface melting models preclude the existence of an orientation dependent surface energy even at high temperatures, for clearly the roughening process may be orientation dependent, as may
the magnitude of the sohd-hquid mterfaclal energy. If anlsotropy exists, then eq.
(1) does not necessarily hold for all surfaces In this case, the minimum requirement for surface nucleation in a bulk specimen is
(7sv)max ~> 7LV + 7SL,

(la)

where (~'SV)max lS the highest value of Tsv corresponding to the surface onentatmn
of maximum energy on the polar 7-plot Thus, it is not necessary that low energy
planes be completely wet by the hqmd, and the posslblhty remains that
(7SV)nun <( 7LV + "/SL ,

(lb)

where (TSV)mln IS the lowest value of surface energy on the "r-plot However, our
purpose is to calculate values of surface energy typical of an "average" lugh-mdex
surface, and by comparing eqs (la) and (lb) above, it Is clear that the average surface energy should be close to 7LV + 7SL, the value given by eq. (2). The main
effect of an amsotroplc 7sv will be that the singular, low energy surfaces may not
roughen or melt below Tin, whereas the high-index surfaces should still show such
a transition.
Eq. (2) reduces the problem of finding 7SV/TLV to one of estimating the magnitude of the ratio 7SL/TLV- The available experimental measurements of 7SL have
been rewewed recently by Jones [9]. The most complete set of 7SL data for the

270

W R Tyson, W A Mdler / Surface free energtes o f sohd metals

metals is that obtained by the homogeneous nucleation experiments of Turnbull

and Cech [10], but these results are generally considered to be low by a significant
factor [9,11 ]. Alternatwely, we have used a combination of other surface energy
ratios to deduce "/SL/"/LV" We begin by defining the relation
"/SL "YSL"/gb
- - - -

- -

- - ,

(3)

')'SV "/gb ')'SV

where 7gb IS the energy of an average (high-angle) gram boundary. The ratio 3'SL/
7gb in pure metals can be otamed by extrapolation of dthedral angle data m binary
alloys [I 1], with the results for pure Zn and A1 being ")'SL/Tgb = 0 44 and 0.47
respectively. Similarly, 7gb/TSV may be obtained from measurements of dihedral
angles at thermally etched grain boundaries m metals (table I). If we take 7SL/
~/gb = 0.45 +- 0 05 and ")'gb/')'SV = 0.33 4 0.04 as typical values for all metals then
a = 0 15 +- 0.03. Combining eqs. (2) and (3), we have

~SL/')'LV = a/(1 - a ) ,

(4)

and, using the above value for a, ')'SL/')'LV = 0.18 4" 0.03. Then, using eq (2),
7SV/TLV = 1.18 -+ 0.03 at the melting point, Tm. This result Lrnphes that the ratio
of solid to hquid surface energy is constant for all of the elements. There is good
reason to expect this to be roughly true for the metallic elements, but it may not
be valid for materials of other bond types such as the covalent metalloids. Constancy of the ratm ')'SV/')'LV depends upon a constant value oftx, and as (3) shows,
a depends upon the ratios ')'SL/')'gb and 796/3'sv- The dthedral angle data point to a
roughly constant value of "~"SL/~gb for both metallic and covalent binding, but thermal etching data have shown that non-metallic materials are usually characterized
by high values o f 7~b/TSV- Thus, somewhat higher values of both a and 7SV/TLV

Table 1
Values of 3'gb/q'SVobtamed from thermal groove angle measurements
Metal

~gb/'rSV

Ag
Au
Co
Cu
8-Fe
Mo
Nb
N1
Pt
Sn
Ta
W

0 35
0 27
0 36
0 32
0 37
0 27
0 34
0 38
0 33
0 24
0 32
038

Rel
161
16]
16,171
16]
16,171
18,191
16,181
16,171
161
161
181
16,18]

W R Tyson, WA Miller / Surface free energies of solid metals

271

might be antlclpated
for the non-metalhc
elements. This pomt ~111 be pursued
elsewhere [8], but m the present work we assume that ~sv/~tv
5 1 18
The suggestion that the magmtudes of the quantltles 7s~ and yLv are related
IS not new. EmpIrIcal or seml-empmcal estimates of the ratlo ysv/yLv are found in
the literature with values ranging from 1.09-1.33
[12,13]. Furthermore, Skapskl
[ 141 has previously proposed eq (2) for the purpose of calculatmg ysv. However,
his numerical results are of little value today, smce they were obtained using
inaccurate theoretlcal values for yLv and ysL By way of contrast, the present
work employs experimental observations to obtain both of these quantltles in order
to calculate ysv at the melting temperature.

3. Estimation of the temperature dependence of 7s~

The temperature dependence
entropy Ssv by the definition
dy&dT=

of the surface free energy IS related to the surface

Ssv .

(5)

The surface entropy

contnbutlons,
WZ.
conf
ssv = s$!j + ssv

may be wrltten

as the sum of vlbratlonal

and configurational

(6)

Theoretical estimates of S$ and SFTf have been reviewed by Tyson [4], who used
crude averages to estimate that Ssv -R per mole of surface atoms, SSV bemg
assumed for slmphclty to be independent of temperature.
The vlbratlonal contrlbutlon Sg@ orlgmates in the altered vlbratlonal modes of
surface atoms compared to atoms m the interior. It IS expected that these modes,
like the bulk modes, will be progressively excited with mcreasmg temperature so
that S$ will vary from zero at 0 K to a maxLmum at a temperature of the order
of the Debye temperature, TD. For metals, TD/T, typically ranges between 0 1
and 0.3 Taking a value of 0.2 as bemg representative and using the reasonable value
atoms
(set
[4] for dlscusslon). we may
(S%)L,, z 0 8R per mole of surface
jpproxlmate
the temperature dependence of S $? with a lmear function rangmg
from zero at 0 K to 0 8 R at T/T,,,
= 0 2,thereafter remammg constant at 0.8 R at
temperatures between 0.2 T,,and the melting pomt
Previous theoretlcal estimates of configuratlonal
entropy, SrGf, lndlcate [4]
that roughening of a high-Index crystal surface typically begins near T/T,,,
= 0.5
entropy
and increases progressively up to T,. The maxLmum configuratlonal
of a completely rough crystallme surface IS estimated as -R per mole of
(S%%X
surface atoms [4]. This value IS m reasonable agreement with the followmg estimate
obtained using the entropy of fusion ASr
At T,,,the surface IS expected to be quite rough and it would seem reasonable
to regard the roughened layer as a liquid of approximately monatomlc thickness

272

W R Tyson, I A Miller / Surface free energies of sohd metals

1.2

~o8

20

I 5

"1

i o ~

~o4
05

~,~

0 m,

-o

0.2

O4

O6

08

T/Tm

Dig 1. Varmt]on of surface free energy and entropy with homologous temperattare TIT m
Hence, the surface entropy at T m is approximately equal to the difference between
hqmd and sohd entropies, 1.e , ASf Typically, z2~Sf~ R per mole for metals, m
agreement with the theoretical surface roughening calculations quoted above. The
configuratlonal entropy must vary with temperature, from a value near zero at
T/Tm = 0.5 to mR at Tm, again, for the purpose of our calculations we shall assume
a hnear variation within this temperature range
We have used eq. (6) to calculate the total surface entropy, based on the assumptions detailed above. Thus, entropy must vary with temperature roughly as shown
m fig. 1. Also included m the figure is a curve showing the temperature dependence
o f the surface energy obtained from S s v using eq. (5), written in the form

"YSV - 3'sv(Tm) = J
T

Ssv
~
dT,

where A is the surface area per mole of surface atoms, which permits entropy to be
expressed on a per umt area basts. For a high-index crystal surface, a reasonable
value for A is [4]
A ~- 1 6 1 2 N I / 3 V 2/3 ,

(7)

where N is Avogadro's number and Vls the molar volume. Fig 1 shows that, for all
metals, 3,(0) - 3'(Tm) ~ R T m / A , for many of the metals the quantity R T m / A corresponds roughly to a 10% change m 3'sv between 0 K and Tin-

4. Values of 3'sv for selected metals

As shown in section 2, 3'sv = 1.18 3'LV at Tin, while m section 3, reasonable
values o f the surface entropy were estimated to permit the calculation of 3'sv at
any temperature below Tm (fig 1) Hence, 3'sv(T) may be deduced from expert-

W R Tyson, WA Mtller/ Surface free energtes ofsohd metals

273

Table 2
Values of surface energy at absolute zero 7SV(0) for selected metals.
Metal

Ag
AI
Au
Be
B1
a-Co
Cu
a-Fe
In
Nl
Sn
TI
W
Zn
Zr

7SV(0) (J/m 2)
From "rLV
(see text)

Expt

0 25 H(O)/A

1 24
1 14
1 50
1 62
0 49
2 51
1 78
2 41
0 70
2 37
0 71
1 98
3 25
0 99
1 90

1 32
1 18
1 54
1 15
0 56
2 16
1 77
2 36
0 67
2 24
0 70
1 92
2 99
0 91
2 05

1 11
1 27
1 42
2 05
0 50
2 16
1 68
2 06
0 72
2 24
0 86
1 75
3 41
0 55
1 92

[]

--

~2-

~ C u

I ---"~

Sn

I00O

2000
T (K]

3000

4000

Fig. 2. Comparison of experimental values of surface energy (see Tyson [4] for original sources)
with calculated values (shown as solid curves) for tungsten, copper, and tin.

274

W R Tyson, W A Mdler / Surface/ree energies o/ sohd metals

mental measurement of 3'LV(Tm) and molar volume V(whlch can be used to obtain
A from eq. (7)) The necessary data have been tabulated by Lang [7] and by Pearson [15], and have been used to obtain 7sv(0) as shown m table 2 for some representative metals for which expermlental 3'sv data are also available The tabulated "experimental" values of 7sv(0) have been extrapolated from experimental 7sv
data at higher temperatures [4] using the surface entropy values deduced m this
paper Finally, for purposes of comparison with another method of calculating
7sv(0), table 2 displays values for 0 25 H(O)/A, where H(0) is the cohesive energy
at absolute zero This expressmn was suggested prewously by Tyson [4] to be a
good estimate of 7sv(0).
Fig. 2 displays the calculated temperature dependence of 7sv for three metals,
shown by the solid hnes, the points show experimental data obtamed from a
variety of authors [4]

5. Discussion and application to the calculation of 7sv for the elements

It is apparent from table 2 that the values of Tsv(0) obtained from ')'LV(Tm)as
outhned m this paper are, on the whole, m good agreement with values of'Ysv(0)
obtained by extrapolation from the temperature of measurement. Furthermore, the
agreement seems to be somewhat better than that achieved by using values obtained
from the cohesive energy. There are two metals for which the three columns of
table 2 show notable discrepancies, VlZ. Be and Zn. In the former case, there IS reason to suspect the experimental result (a logical suspicion m view of typical experimental scatter, see fig. 2) although the error may not be as large as would be predicted from the correlation with cohesive energy. The reason for the failure of the
cohesive energy correlation in the case of Zn will be discussed elsewhere [8]. Since
the calculation of 7sv from 7LV appears to yield rehable results, we have prepared
m table 3 estimates of 3'sv(Tm) for all elements for which dependable experimental
data on 3'LV exast Also included in table 3 are values of R T m / A , which can be used
with fig 1 to obtain 3'(T) at any temperature of interest.
It would be useful to compare our estimates of Ssv with experimental data, but
unfortunately It ts not possible to quote a rehable experimental value for Ssv due
to the limitations inherent in existing measurement techmques. It is clear from fig
2, however, that the current predictions are not unreasonable.
In conclusion, it has been shown that good values of Tsv(Tm) may be derived
from 7LV(Tm), and that 7sv may be deduced at lower temperatures from 7sv(Tm)
requiring m addition only a value for the molar volume V(assumed to be constant
at the room temperature level m this work) It is difficult at present to place a
figure on the rehablhty of the results in xaew of the scarcity of accurate experimental values of 7sv- However, ~t ~s felt that the values of 7sv estimated m this way are
more accurrate than other presently available estimates of this quantity, and that

W R Tyson, I A Mdler / Surface free energtes ofsohd metals

275

Table 3
Calculated values of surface energy 3,sv(Tm) for the elements for which rehable 7LV(Tm) data
exist, and values of R Tm/A
Element

Ag
A1
Au
B
Ba
Be
B1
Ca
Cd
Co
Cr
Cs
Cu
Fe
Ga
Ge
Hf
Hg
In
Ir
K
L1
Mg
Mn
Mo

3,sv(Tm)

RTm/A

(J/m 2)

(J/m 2)

1 086
1 020
1 333
1 060
0 326
1 298
0 446
0 425
0 696
2 218
2 006
0 084
1 566
2 123
0.845
0 748
1 923
0 58
0 658
2 655
0 129
0472
0 688
1 298
2 510

0 160
0 123
0 173
t 0 55
0 054
0 330
0 043
0 077
0 066
0 304
0 348
0 011
0 224
0 294
0 036
0 129
0 270
0 025
0.042
0 393
0 016
0 050
0 097
0 245
0 397

Element

Na
Nb
Nd
N1
Os
Pb
Pd
Pt
Rb
Re
Ru
Rh
Sb
SI
Sn
Sr
Ta
T~
T1
U
V
W
Zn
Zr

~,sv(Tm)

RTm/A

(J/m 2)

(J/m 2)

0 234
2 313
0 812
2 080
2 950
0 540
1 743
2 203
0 104
3 133
2 655
2 325
0461
0 94
0 661
0 358
2493
1 749
0 550
1 780
2 301
2 765
0 896
1 687

0 027
0 342
0 090
0 300
0 489
0 053
0 260
0 286
0 013
0493
0 388
0 334
0 136
0 195
0 048
0 061
0 409
0 240
0.052
0 159
0 321
0 500
0 097
0 222

t h e m e t h o d is a p p h c a b l e t o d e d u c e 7 s v ( T ) for the large n u m b e r o f e l e m e n t s s h o w n

m table 3 for w h i c h rehable h q u l d surface t e n s i o n d a t a exist.

Acknowledgements
The a u t h o r s are grateful t o t h e reviewer for c o n s t r u c t w e suggestions o n t h e presentation.

References
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276
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[10]
[11]
[12]
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[14]
[ 15 ]
[16]
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[18]
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